CN107698842A - The new application of alkoxy benzophenone - Google Patents
The new application of alkoxy benzophenone Download PDFInfo
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- CN107698842A CN107698842A CN201710937162.1A CN201710937162A CN107698842A CN 107698842 A CN107698842 A CN 107698842A CN 201710937162 A CN201710937162 A CN 201710937162A CN 107698842 A CN107698842 A CN 107698842A
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- alkoxy
- based materials
- polyolefin based
- benzophenone
- new application
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses the new application of alkoxy benzophenone, one or more of crosslinkings that alkoxy benzophenone is used in polyolefin based materials, the blend of polyolefin based materials, the copolymer of polyolefin based materials and high polymer material containing above-mentioned material as light trigger, the alkoxy benzophenone have formula：
Description
Technical field
The invention belongs to photocuring synthesis technical field, and in particular to the new application of alkoxy benzophenone.
Background technology
Polyethylene (PE) and polypropylene (PP) have good electrical insulating property and the performance such as easily processed into type, are most to send out
The thermoplastic of future is opened up, is had a wide range of applications in industry, agricultural and daily life.Yet with its molecular structure
Nonpolar and its crystallinity, its resistance to elevated temperatures is poor, mechanical property is insufficient and melt strength is low, causes the device in thermoforming
Wall thickness is uneven, extrusion coated calendering when, the problems such as abscess collapses when there is edge curl, contraction and extrusion foaming, it is impossible to
Meet the requirement of actual use.In addition, its dyeability, cementability, antistatic behaviour, hydrophily and with polar polymer and inorganic
Compatibility, the compatibility of filler are poor, limit further popularization and application.In order to overcome disadvantages mentioned above, people are to polyethylene
Substantial amounts of research work has been done with polyacrylic modification.It is cross-linking modified to polyethylene and polypropylene progress to be allowed to become energy high temperature resistant
Thermosetting plastics to improve its use value be one of target that countries in the world polymeric materials science man pursues.Polyethylene
Cross-linking method mainly has 3 kinds：High-energy radiation crosslinking, chemical crosslinking (peroxide method and silane thermal decomposition process) and ultraviolet light cross-linking.It is ultraviolet
Optical cross-linking method is to start to realize the new cross-linking method of commercial Application in recent years, by its property of cross-linking modified polyethylene and polypropylene
It can significantly be improved, not only significantly improve mechanical property, environmental stress cracking resistance, resistance to corrosive chemicals
The combination properties such as energy, creep resistance and electrical property, and be readily apparent that to improve temperature resistant grade, the heat-resisting temperature of polyethylene can be made
Degree brings up to more than 100 DEG C from 70 DEG C, so as to widen the application of polyethylene significantly.Photocuring technology (ultraviolet light cross-linking)
It is a kind of new green environmental protection technique, its efficiency of initiation is high, and speed is fast, high financial profit.From nineteen sixty-eight Germany Bayer company
Since curable wood coating is developed in success, photocuring technology is had been widely used in coating, ink, adhesive, microelectronics, gear division
The field such as reparation and biomaterial.The photocuring technology in China is continued for high speed development, it has also become is only second to the U.S. and Japan
Photocuring raw material and product big producer.Light trigger is also known as sensitising agent or light curing agent, is that one kind can be in ultraviolet light
Area or visible region absorb the energy of certain wavelength, produce free radical, cation etc., so as to trigger the solidification of monomer polymerization crosslinking
Compound.Light trigger is an important component in photocuring system.
Light trigger currently used for polyethylene crosslinking can be divided into two major classes：Crack type photoinitiator and hydrogen-abstraction light draw
Send out agent.After crack type photoinitiator absorption UV energy transits to excitation state, scission of link itself produces free radical.This kind of initiator
Mainly there are styrax class compound and benzil acetal and acetophenone derivs.Hydrogen-capture-type light initiator mainly have benzophenone,
The aryl ketones such as anthraquinone, thioxanthone.This photoinitiator follows photo-reduction mechanism, need to there is hydrogen atom donor (DH) mating reaction.
Light trigger is excited to singlet state, then transits to more stable triplet (T3), abstract hydrogen atoms by being passed through between being
Post-passivation；And hydrogen donor then forms Active Radicals Produced initiation reaction.Document (hen Y.L., Ranby
B..J.Polym.Sci.PartA:Polym.Chem.[J],a.1989,27:4 051—4 075；b.1989,27:4 077—4
086；c.1990,28:1847-1859) efficiency that 18 kinds of different types of light triggers are triggered with polyethylene photo-crosslinking is reported
Compare, find hydrogen-abstraction than crack type photoinitiator efficiency high, and the efficiency of initiation highest of benzophenone.Document
(Zamotaev P.V.,Chodak I..Angew.M akromol.Chem.[J],1993,210:119-128) research knot
Fruit shows that the hydrogen-capture-type light initiators such as benzophenone, anthraquinone, xanthone are the maximally effective initiations of polyethylene photo-crosslinking
Agent.However, these light triggers when being used alone, trigger cross-linked speed relatively low, also, existing light trigger and poly- second
Alkene or polyacrylic compatibility are poor, cause the tensile strength deficiency of cross-linked material.
The content of the invention
The present invention is used in view of the shortcomings of the prior art, providing a kind of alkoxy benzophenone compound as light trigger
The new application of the modified crosslinking of polyolefin based materials.
Concrete technical scheme of the present invention is as follows：
The new application of alkoxy benzophenone, alkoxy benzophenone are used for polyolefin based materials, polyolefin as light trigger
One or more in the blend of class material, the copolymer of polyolefin based materials and high polymer material containing above-mentioned material
Crosslinking.The polyolefin based materials are selected from low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), high density
Polyethylene (HDPE), polypropylene (PP), Kynoar (PVDF), ethene and ethenol copolymer (EVOH), ethene and propylene
One or more in copolymer.
The alkoxy benzophenone has formula：OR
The alkoxy of C1-C10 straight or brancheds is represented, preferably represents C2-C8 alkoxy, further preferred OR is n-octyloxy, more
It is preferred that 4- n-octyloxies, structure are as follows：
The OR groups can be that any position substitutes, it is preferred that OR substitutions position is 4.
Another object of the present invention is to provide a kind of photo curable composition, including polyolefin based materials or itself and its
The blend of his high polymer material and at least one alkoxy benzophenone with formula：OR represents the alkoxy of C1-C10 straight or brancheds, preferably represents C2-
C8 alkoxy, further preferred OR are n-octyloxy, more preferably 4- n-octyloxies.
The OR groups can be that any position substitutes, it is preferred that OR substitutions position is 4.
Above-mentioned photo curable composition can with the art receive other additives, as antioxidant, crosslinking agent,
Ultraviolet absorber, light stabilizer, fire retardant, fluorescent whitening agent, antistatic additive, hydrolysis-resisting agent etc.
The Masterbatch for the various materials that above-mentioned photo curable composition can be made into.
Advantage of the present invention：
The new application of alkoxy benzophenone disclosed by the invention provides polyolefin based materials ultraviolet light cross-linking under prior art
Modified effect, compared with other benzophenone compounds, alkoxy benzophenone class compound and polyolefin based materials phase
Capacitive is good, and cross-linking efficiency is high, and cross-linking products, tensile property is good, has more superior mechanical property and heat resistance.
Embodiment
Used term in the present invention, unless otherwise indicated, typically there are those of ordinary skill in the art generally to manage
The implication of solution.
The present invention is described in further detail with reference to specific embodiment and with reference to data.It should be understood that the embodiment is
In order to demonstrate the invention, rather than the scope that limit the invention in any way.
In the examples below, the various processes and method not being described in detail are conventional methods as known in the art.Under
Material used in example, reagent, device, instrument, equipment etc. are stated, unless otherwise specified, is commercially obtained.
With reference to specific embodiment, the present invention is further described.
Embodiment 1
The present embodiment has investigated benzophenone (BP), dodecyl benzophenone (BP-D), (the 4- hydroxyl hexichol of decanedioic acid two respectively
Ketone) ester (BP-S), 2 hydroxyl -4- oxy-octyl benzophenones (UV531), 4- oxy-octyl benzophenones, 4- methoxyl group hexichol
Ketone, 4- n-decyloxies benzophenone are to the modified crosslinking ability of polyethylene.Above-claimed cpd can pass through commercially available or customization
Synthesis, also refers to document《Ultraviolet absorbent UV-531 synthesising process research》(Gu Shuo, Peng Guangrong, chemical industry in Jiangsu Province, 2008
October, the phase of volume 36 the 5th, 26-27 pages) disclosed in synthetic method be prepared.
Experimental procedure：
By 1 part of light trigger and 100 parts of polyethylene (parts by weight), it is kneaded by extruder, is set subsequently into ultraviolet radiation
The standby molten state that carries out is irradiated 10 seconds, and ultraviolet source is high-pressure sodium lamp, power 2kw, crosslinking, flat board sulphur is then used at 150 DEG C
Change machine is hot pressed into 1mm sheet material.
Sample detection：
(1) gel content：Photo crosslinked polyethylene sample is changed once new after being extracted in the dimethylbenzene of micro-boiling 48 hours, 24 hours
Fresh dimethylbenzene, to constant weight under 75 DEG C of vacuum drying after acetone cleans.Gel content is calculated by following formula：
Gel%=(W/W0) × 100%
W0Sample weight before-extracting；Xerogel weight after W- extractings.Each sample does three parallel samples, work of averaging
For the gel content value of the sample.As a result it is as shown in table 1.
The gel content of table 1 investigates result
| BP | BP-D | BP-S | 531 | 4- oxy-octyl benzophenones | 4- methoxy benzophenones | 4- n-decyloxy benzophenone | |
| Gel content | 45% | 55% | 58% | 57% | 82% | 61% | 71% |
As a result alkoxy benzophenone class compound of the present invention, the particularly conduct of 4- oxy-octyl benzophenones are shown
Light trigger, the gel content of its cross-linking products are significantly increased relative to the light trigger of prior art, illustrate the just pungent oxygen of 4-
Base benzophenone has stronger cross-linking properties, light trigger efficiency high.
(2) thermal ageing test：
Sample is placed in 158 DEG C of thermal aging ovens and places 168h, then surveys tensile strength and elongation at break.
Tensile property：Provide to test according to GB/T 1040-2006, thickness be 1.0 ± 0.1mm, rate of extension for 200 ±
50mm/min。
Apparatus selection Shimadzu Corporation DCS-5000 type tensilons.Each sample does 5 Duplicate Samples, averages.Knot
Fruit is as shown in table 2.
The tensile property of table 2 investigates result
As a result show alkoxy benzophenone class compound of the present invention, particularly 4- oxy-octyl benzophenones with gathering
Ethene has good compatibility, the direct combination degree of vinyl polymer can be advantageously promoted, so as to improve polyethylene
The tensile strength of material.Due to the molecular side chain group property of alkoxy benzophenone, make the simultaneous of its molecule and polyethylene molecule
Capacitive greatly improves, so that it is able to uniformly disperse in polyethylene, its crosslinking ability has obtained more fully playing,
And other other initiators of prior art light can not be accomplished uniformly to disperse because poor with polyethylene compatible, can only be mixed with physics
The form of conjunction is present, therefore greatly constrains its crosslinking ability.
Claims (9)
1. the new application of alkoxy benzophenone, it is characterised in that alkoxy benzophenone is used for TPO as light trigger
In material, the blend of polyolefin based materials, the copolymer of polyolefin based materials and high polymer material containing above-mentioned material
One or more of crosslinkings.
2. new application according to claim 1, it is characterised in that the polyolefin based materials are selected from low density polyethylene (LDPE), line
Property low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, Kynoar, ethene and ethenol copolymer, ethene and propylene are total to
One or more in polymers.
3. new application according to claim 1, it is characterised in that the alkoxy benzophenone has formula：
OR represents the alkoxy of C1-C10 straight or brancheds.
4. new application according to claim 3, it is characterised in that the OR substitutions position is 4.
5. new application according to claim 3, it is characterised in that the OR is 4- n-octyloxies.
A kind of 6. photo curable composition, it is characterised in that the blend, poly- including polyolefin based materials, polyolefin based materials
One or more of and at least one in the copolymer of olefines material and the high polymer material containing above-mentioned material have
The alkoxy benzophenone of formula：OR represents C1-C10 straight chains
Or the alkoxy of side chain.
7. composition according to claim 6, it is characterised in that the polyolefin based materials are selected from low density polyethylene (LDPE), line
Property low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, Kynoar, ethene and ethenol copolymer, ethene and propylene are total to
One or more in polymers.
8. composition according to claim 6, it is characterised in that the OR substitutions position is 4.
9. composition according to claim 6, it is characterised in that the OR is 4- n-octyloxies.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710937162.1A CN107698842A (en) | 2017-10-10 | 2017-10-10 | The new application of alkoxy benzophenone |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710937162.1A CN107698842A (en) | 2017-10-10 | 2017-10-10 | The new application of alkoxy benzophenone |
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| CN107698842A true CN107698842A (en) | 2018-02-16 |
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| CN201710937162.1A Withdrawn CN107698842A (en) | 2017-10-10 | 2017-10-10 | The new application of alkoxy benzophenone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776586A (en) * | 2019-10-24 | 2020-02-11 | 安庆飞凯新材料有限公司 | Preparation method and application of alkoxy benzanthrone photoinitiator |
-
2017
- 2017-10-10 CN CN201710937162.1A patent/CN107698842A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776586A (en) * | 2019-10-24 | 2020-02-11 | 安庆飞凯新材料有限公司 | Preparation method and application of alkoxy benzanthrone photoinitiator |
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Application publication date: 20180216 |
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